Sub-molecular structural relaxation at a physisorbed interface with monolayer organic single-crystal semiconductors
Abstract
Arranging molecules into highly symmetric, topological crystal structures has been recognized as the best approach to functionalize electronic properties in molecular crystals, where the constituent molecules have been assumed to be rigid in shape. Here, in striking contrast, we demonstrate that the molecules in a monolayer organic crystal can undergo a significant deformation in proximity to the substrate, which is reflected by an asymmetry in the electron density profile. X-ray reflectivity and X-ray absorption spectroscopies in conjunction with density-functional theory calculations reveal that the highly planarized π-core are deformed into a bent shape, while the bulk lattice parameters are maintained. The molecular shape change is found to be perfectly suppressed in a bilayer single crystal, which leads to a 40% increase in mobility in the bilayer crystal. Our finding of a unique, sub-molecular scale shape change in monolayer single crystals can offer possibilities for functionalizing electrical properties via nano-scale physisorption.
- Authors:
-
- Univ. of Tokyo (Japan). Dept. of Advanced Material Science; National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan)
- Osaka Univ. (Japan); Tohoku Univ., Sendai (Japan). Dept. of Physics
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- Hiroshima Univ. (Japan). Dept. of Chemistry
- Univ. of Tsukuba (Japan)
- Univ. of Tokyo (Japan). Dept. of Advanced Material Science
- Tohoku Univ., Sendai (Japan). Dept. of Physics
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1605375
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Communications Physics
- Additional Journal Information:
- Journal Volume: 3; Journal Issue: 1; Journal ID: ISSN 2399-3650
- Publisher:
- Springer Nature
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Yamamura, Akifumi, Fujii, Hiromasa, Ogasawara, Hirohito, Nordlund, Dennis, Takahashi, Osamu, Kishi, Yuutaro, Ishii, Hiroyuki, Kobayashi, Nobuhiko, Niitsu, Naoyuki, Blülle, Balthasar, Okamoto, Toshihiro, Wakabayashi, Yusuke, Watanabe, Shun, and Takeya, Jun. Sub-molecular structural relaxation at a physisorbed interface with monolayer organic single-crystal semiconductors. United States: N. p., 2020.
Web. doi:10.1038/s42005-020-0285-7.
Yamamura, Akifumi, Fujii, Hiromasa, Ogasawara, Hirohito, Nordlund, Dennis, Takahashi, Osamu, Kishi, Yuutaro, Ishii, Hiroyuki, Kobayashi, Nobuhiko, Niitsu, Naoyuki, Blülle, Balthasar, Okamoto, Toshihiro, Wakabayashi, Yusuke, Watanabe, Shun, & Takeya, Jun. Sub-molecular structural relaxation at a physisorbed interface with monolayer organic single-crystal semiconductors. United States. https://doi.org/10.1038/s42005-020-0285-7
Yamamura, Akifumi, Fujii, Hiromasa, Ogasawara, Hirohito, Nordlund, Dennis, Takahashi, Osamu, Kishi, Yuutaro, Ishii, Hiroyuki, Kobayashi, Nobuhiko, Niitsu, Naoyuki, Blülle, Balthasar, Okamoto, Toshihiro, Wakabayashi, Yusuke, Watanabe, Shun, and Takeya, Jun. Thu .
"Sub-molecular structural relaxation at a physisorbed interface with monolayer organic single-crystal semiconductors". United States. https://doi.org/10.1038/s42005-020-0285-7. https://www.osti.gov/servlets/purl/1605375.
@article{osti_1605375,
title = {Sub-molecular structural relaxation at a physisorbed interface with monolayer organic single-crystal semiconductors},
author = {Yamamura, Akifumi and Fujii, Hiromasa and Ogasawara, Hirohito and Nordlund, Dennis and Takahashi, Osamu and Kishi, Yuutaro and Ishii, Hiroyuki and Kobayashi, Nobuhiko and Niitsu, Naoyuki and Blülle, Balthasar and Okamoto, Toshihiro and Wakabayashi, Yusuke and Watanabe, Shun and Takeya, Jun},
abstractNote = {Arranging molecules into highly symmetric, topological crystal structures has been recognized as the best approach to functionalize electronic properties in molecular crystals, where the constituent molecules have been assumed to be rigid in shape. Here, in striking contrast, we demonstrate that the molecules in a monolayer organic crystal can undergo a significant deformation in proximity to the substrate, which is reflected by an asymmetry in the electron density profile. X-ray reflectivity and X-ray absorption spectroscopies in conjunction with density-functional theory calculations reveal that the highly planarized π-core are deformed into a bent shape, while the bulk lattice parameters are maintained. The molecular shape change is found to be perfectly suppressed in a bilayer single crystal, which leads to a 40% increase in mobility in the bilayer crystal. Our finding of a unique, sub-molecular scale shape change in monolayer single crystals can offer possibilities for functionalizing electrical properties via nano-scale physisorption.},
doi = {10.1038/s42005-020-0285-7},
journal = {Communications Physics},
number = 1,
volume = 3,
place = {United States},
year = {Thu Jan 23 00:00:00 EST 2020},
month = {Thu Jan 23 00:00:00 EST 2020}
}
Web of Science
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